DE60119188T2 - Process for the preparation of an epoxycyclododecane compound - Google Patents

Description

BACKGROUND THE INVENTION

1st area the invention

The The present invention relates to a process for the preparation of a Epoxycyclododecane compound. In particular, the present invention relates Invention A process for preparing an epoxycyclododecane compound by catalytic and selective hydrogenation of double bonds of 1,2-epoxy-5,9-cyclododecadiene.

A Epoxycyclododecane compound can find use not only for Preparation of a resin component for paints and adhesives, but also for the preparation of a lactam compound, a lactone compound or a dibasic carboxylic acid by one of the epoxycyclododecane according to a conventional method derived cyclododecanone, thus providing an important intermediate for polyamide 12 and polyester, the useful Materials for the production of synthetic resins and synthetic fibers are.

2. Description of the state of the technique

It is known to be an epoxycyclododecane compound by catalytic Reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a platinum group metal-containing catalyst.

For example Soviet (SU) Patent No. 380,650 discloses a method for the synthesis of an epoxycyclododecane compound by reduction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in a cyclohexane medium in the presence of a catalytic component containing a platinum group metal (a metal of Group VIII of the Periodic Table) on an alumina or activated carbon existing carrier comprises, at a reaction temperature of 70 to 200 ° C under a Hydrogen gas pressure of 101 325 to 263 445 kPa (100 to 260 atm). However, in this method, the yield of the target epoxycyclododecane compound is with 82 to 95% unsatisfactory. Furthermore, this method is disadvantageous inasmuch as the necessary amount of catalyst based on the Amount of 1,2-epoxy-5,9-cyclododecadiene involved in the reaction process supplied is, is too high.

Further reveals the writing "Russian Journal of General Chemistry ", Vol. 67, no. 6 (1997), pp. 921-926, a result of a reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a catalyst comprising a catalytic Component comprising a platinum group metal (e.g., palladium or platinum) on a charcoal, alumina or silica gel comprising carrier component includes. In one embodiment of the process, the reaction was carried out in the presence of a catalyst, comprising palladium on an activated carbon, alumina or silica gel comprehensive carrier, at a reaction temperature of 30 to 90 ° C under a hydrogen gas pressure from 0.1 to 4.0 MPa, and the target epoxycyclododecane compound was in a yield from 80 to 99% received. In another embodiment, the reaction became in the presence of a catalyst comprising platinum on a silica gel support a reaction temperature of 50 ° C. under a hydrogen gas pressure of 1.3 to 2.5 MPa, and the target epoxycyclododecane compound was in a yield of 84% received. However, this report contains nothing about the Life of the catalyst.

The GB-A-1230288 discloses the hydrogenation of 1,2-epoxy-5,9-cyclododecadiene by adding 1 g of 5% Pt on C to 50 g of the epoxy compound. The effluent contained 98% epoxycyclododecane.

As a general rule it is in the industrial use of a catalyst, the a platinum group metal - in which it is an expensive precious metal - contains, necessary that the resulting Catalyst allows to produce the target product in high yield; that the catalytic reaction be carried out at a high reaction rate can and that the resulting catalyst has a long life having.

The Literature and the patent publications However, the prior art does not teach or suggest how to lend the catalyst a long life.

SUMMARY THE INVENTION

A Object of the present invention is to provide a Process involving the industrial production of an epoxycyclododecane compound in high yield at a high reaction rate by a reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a Catalyst, which has a long life, allows.

The The above object can by the method according to present Invention solved become.

The Process according to the present invention Invention for producing an epoxycyclododecane compound the hydrogenation of 1,2-epoxy-5,9-cyclododecadiene with a hydrogen gas in the presence of a platinum group metal-containing catalyst, wherein the hydrogen gas has a pressure of 0.8 to 9 MPa and wherein the platinum group metal-containing catalyst comprises a platinum-containing catalytic component on an inert carrier component, which the latter consists of activated carbon, wherein the platinum contained catalytic Component in an amount based on the platinum content used which is 0.000001 to 0.0005 times the molar amount of 1,2-epoxy-5,9-cyclododecadiene is.

at the method according to present Invention for the preparation of an epoxycyclododecane compound the hydrogen gas pressure for the hydrogenation in the range of 3 to 7 MPa.

at the method according to present Invention for producing an epoxycyclododecane compound the hydrogenation under a hydrogen gas pressure of 0.8 to 9 MPa carried out at a temperature above 50 ° C.

at the method according to present Invention for the preparation of an epoxycyclododecane compound the platinum-containing catalytic component in an amount based to the platinum content, from 0.1 to 10 wt% before, based on the Weight of the inert carrier component.

DESCRIPTION THE PREFERRED EMBODIMENTS

The 1,2-epoxy-5,9-cyclododecadiene, which is used as starting material for the process according to the present Invention can be used, can be, for example, by Epoxidizing a cyclododecatriene with an organic carboxylic acid and Produce hydrogen peroxide. In the resulting 1,2-epoxy-5,9-cyclododecadiene can the epoxy group and the double bond in cis form, trans form or in any other form.

For the procedure according to the present Invention may be a commercial one 1,2-epoxy-5,9-cyclododecadiene without purification by distillation etc. or after purification by distillation etc. If the compound is a synthetic product, the compound becomes preferably after purification by distillation, etc. used.

Of the platinum-containing catalyst which is suitable for the present invention Can be used, is preferably selected from solid catalysts, preferably particulate solid catalysts, more preferably particulate solid catalysts having an average particle size of several μm to several One hundred microns, in particular 10 to 300 μm, comprising a catalytic component comprising a platinum-containing Compound and carried on an inert support.

Of the inert carrier for the Catalyst is formed from activated carbon.

The platinum-containing catalytic component is preferably in one Amount, based on the platinum content, of 0.1 to 10 wt.%, More preferably 0.2 to 8% by weight, based on the weight of the inert support component in front. In the case of the catalyst, the platinum-containing catalytic component on the surface and / or inside the inert carrier component be worn.

at the method according to present Invention, the specific platinum-containing catalyst has a long Life on.

In the hydrogenation reaction according to the process of the present invention, the platinum-containing catalyst is used in a molar amount, based on the platinum content, which is 0.000005 to 0.0004 times the molar amount of the 1,2-epoxy starting material used. 5,9-cyclododecadiene is. If the amount of catalyst is too small, the time required to complete the reaction may become too long. Further, the use of the catalyst in excessive amount may decrease the yield of the target product.

at the catalytic reaction according to the method according to present Invention, a reaction medium is not always necessary. When the reaction medium is used are e.g. Hydrocarbons such as n-hexane, n-heptane, n-tetradecane and cyclohexane; Ethers such as tetrahydrofuran and dioxane; Alcohols such as methyl alcohol, ethyl alcohol, tert-butyl alcohol and tert-amyl alcohol; and esters such as ethyl acetate and butyl acetate. These organic compounds for the reaction medium can for themselves alone or as a mixture of two or more of these compounds be used. The reaction medium is preferably in an amount which is 0 to 20 times, more preferably 0 to 10 times the weight of the the reaction used is 1,2-epoxy-5,9-cyclododecadiene.

at the method according to present Invention, the hydrogenation for the double bonds of 1,2-epoxy-5,9-cyclododecadiene in the presence of the platinum-containing catalyst under a hydrogen gas pressure from 0.8 to 9 MPa, preferably from 1 to 8 MPa, more preferably from 3 to 7 MPa performed. In the method according to the present In the invention, the reaction temperature is not particularly limited. Preferably, the reaction temperature is adjusted to a level which is preferably above 50 ° C more preferably in a range of 70 to 200 ° C, even more preferably in a range of 70 to 150 ° C.

If the reaction hydrogen gas pressure and the reaction temperature too are low, it can be undesirable take a long time for the reaction to complete and the yield a by-product consisting of cyclododecanol may be increased while the yield of the target compound can be reduced. Next: if the reaction hydrogen gas pressure and the reaction temperature too are high, can be an undesirable Reduction of the target compound favors and thus the yield the target compound can be reduced.

at the method according to present Invention becomes after completion of the hydrogenation reaction process the catalyst is separated from the resulting reaction mixture and recovered, and the target epoxycyclododecane is released from the remaining reaction mixture by a purification process, e.g. one distillative process, isolated. It becomes an epoxycyclododecane obtained of high purity. In the case that the resulting Epoxycyclododecane is further converted into cyclododecanone or a dodecanedioic acid, may after removal of the catalyst from the reaction mixture the remaining reaction mixture of an isomerization reaction of epoxycyclododecane or an oxidation reaction of epoxycyclododecane, which is contained in the remaining reaction mixture subjected become.

EXAMPLES

The The present invention will be further illustrated by the following examples.

example 1

An SUS stainless steel autoclave with a capacity of 100 ml equipped with a stirrer was charged with 20 g (0.112 mol) of 1,2-epoxy-5,9-cyclododecadiene and 0.08 g of platinum-containing catalyst particles comprising 5% by weight. a platinum-containing catalytic component on an activated carbon support (Platinatommenge: 0.0102 mmol, water content: 50 wt.%, BET specific surface area: 1200 m ² / g, a product of the company NE CHEMCAT), charged.

The Inside of the autoclave was pressurized with a hydrogen gas of 5 MPa pressurized at room temperature. Then the Reaction mixture heated to a temperature of 70 ° C and at the temperature mentioned above under the above mentioned Pressure stirred, until no hydrogen uptake of the reaction mixture more detectable was. After completion of the reaction, the reaction mixture became Room temperature cooled, the catalyst was removed from the reaction mixture by filtration removed and the remaining reaction mixture was subjected to gas chromatography Subjected to analysis.

The results of the analysis confirmed that the starting 1,2-epoxy-5,9-cyclododecadiene was completely consumed, that the target epoxycyclododecane (hereinafter referred to as ECD) was produced in 99.6 mol% yield and that as by-products cyclododecanone (hereinafter referred to as CDON) in a yield of 0.04 mol%, cyclododecanol (hereinafter referred to as CDOL) in a yield of 0.2 mol% and cyclododecane (hereinafter referred to as CDAN) in a yield of 0.04 mol% were obtained.

Examples 2 to 4 and Comparative Examples 1 to 6

In each of Examples 2 to 4 and Comparative Examples 1 to 6 was the Epoxycyclododecan after the same procedure as prepared in Example 1, except that the type of catalyst, the amount of catalyst, the reaction temperature, the hydrogen gas pressure and the reaction time according to the table 1 were set. The analysis was carried out in the same way as in Example 1.

The Results are shown in Table 1.

Example 5

One SUS stainless steel autoclave with a capacity of 1000 ml, which with a stirrer and a filter disposed on the exit side for a liquid fraction, was charged with 500 g (2.8 mol) of 1,2-epoxy-5,9-cyclododecadiene and catalyst particles, comprising 5% by weight of a platinum-containing catalytic component on activated carbon carrier particles (Platinate amount: 0.128 mmol, water content: 50% by weight, a product of Company N. E. CHEMCAT). The interior of the autoclave was pressurized with a hydrogen gas to a pressure of 5 MPa. The reaction mixture in the autoclave was then heated to a temperature of 130 ° C heated and at the above mentioned Temperature below the above Pressure for Stirred for 2 hours.

To Termination of the reaction became the resulting reaction liquid fraction withdrawn through the filter from the autoclave and the same analysis as in Example 1 subjected.

in the Result was confirmed that the starting 1,2-epoxy-5,9-cyclododecadiene is completely consumed was that the yield of ECD was 99.2 mol% and that as by-products CDON in a yield of 0.06 mol%, CDOL in a yield of 0.70 mol% and CDAN were obtained in a yield of 0.04 mol%.

thereupon became the autoclave in which the filtered catalyst remained with 500 g (2.8 mol) of fresh 1,2-epoxy-5,9-cyclododecadiene charged, the reaction mixture was a reaction process at a temperature of 130 ° C under a hydrogen gas pressure of 5 MPa for 2 hours. After completion the reaction process became the resulting reaction liquid fraction withdrawn through the filter from the autoclave and the same analysis as in Example 1 subjected. The above-mentioned operations were repeated 15 times. The test results are shown in Table 2. In the fifteenth Reaction process, the starting 1,2-epoxy-5,9-cyclododecadiene was completely consumed, and in the withdrawn reaction liquid fraction was no intermediate product, namely epoxycyclododecene (which will be referred to below as ECD '), found.

The results are shown in Table 2. Table 2

[Annotation]

• Reaction conditions: ECD "(1,2-epoxy-5,9-cyclododecadiene): 500 G,
• Catalyst: 5 wt.% Pt / activated carbon (AC) 1.0 g
• Temperature: 130 ° C
• Pressure: 5 MPa
• Time: 120 min.

Comparative Example 7

The same repeated reactions were carried out as in Example 5, except that the 1000 ml autoclave was replaced with a 100 ml capacity SUS stainless steel autoclave equipped with a stirrer and a filter; that a catalyst comprising a catalyst component in an amount of 0.5% by weight, based on the platinum atoms, on alumina carrier particles in an amount of 0.2 g was used; that 1,2-epoxy-5,9-cyclododecadiene was used in an amount of 20%; that the reaction temperature was changed to 140 ° C and that the repetition number of the Reaction was 10.

The Results are shown in Table 3.

Table 3

[Annotation]

• ECD ": 1,2-epoxy-5,9-cyclododecadiene
• Reaction conditions: ECD ": 20 g, 0.5% by weight Pt / alumina catalyst: 0.2 g,
• Temperature: 140 ° C,
• Pressure: 5 MPa,
• Time: 120 min.

Comparative Example 8

It the same reactions and analyzes were carried out as in Example 5, except that the catalyst contains 5% by weight of a Pd-containing one catalytic component on activated carbon particles included; that the reaction temperature is 50 ° C was and that the reaction time was 4 hours. The results are in Table 4.

in the fifth Reaction process left a large amount (36.2 mol%) of unreacted ECD ".

Table 4

[Annotation]

• AC ... activated carbon
• ECD ": 1,2-epoxy-5,9-cyclododecadiene
• Reaction conditions: ECD ": 500 g,
• Catalyst: 5% by weight Pd / AC: 0.5 g,
• Temperature: 50 ° C,
• Pressure: 5 MPa,
• Time: 240 min.

The Process according to the present invention Invention allows the preparation of an epoxycyclododecane compound by a catalytic hydrogenation reaction of 1,2-epoxy-5,9-cyclododecadiene at a high reaction rate in a high yield. The specific one platinum catalyst for the method according to the present Invention has a long life in practical use, and thus the method of the present invention shows a high industrial availability.

Claims (5)

Process for the preparation of an epoxycyclododecane compound, comprising the hydrogenation of 1,2-epoxy-5,9-cyclododecadiene with a Hydrogen gas in the presence of a platinum group metal-containing Catalyst, wherein the hydrogen gas has a pressure of 0.8 to 9 MPa, and wherein the platinum group metal-containing catalyst a platinum-containing catalytic component on an inert support component which latter consists of activated carbon, wherein the platinum contained catalytic component in an amount related On the platinum content, the 0.000005 to 0.0004-fold is used the molar amount of 1,2-epoxy-5,9-cyclododecadiene. Process for the preparation of an epoxycyclododecane compound according to claim 1, wherein the hydrogen gas pressure for the hydrogenation in the range from 3 to 7 MPa. Process for the preparation of an epoxycyclododecane compound according to claim 1, wherein the hydrogenation is carried out under a hydrogen gas pressure from 0.8 to 9 MPa at a temperature above 50 ° C. Process for the preparation of an epoxycyclododecane compound according to one of the claims 1 to 3, wherein the platinum-containing catalytic component in a Amount, based on the platinum content, from 0.1 to 10 wt .-%, present is based on the weight of the inert carrier component. Process for the preparation of an epoxycyclododecane compound according to one of the claims 1 to 4, wherein the hydrogenation reaction of 1,2-epoxy-5,9-cyclododecadiene is carried out in the absence of a reaction medium.